JPH02501309A - heterocyclic compound - Google Patents

Abstract

PCT No. PCT/CH88/00107 Sec. 371 Date Feb. 14, 1989 Sec. 102(e) Date Feb. 14, 1989 PCT Filed Jun. 16, 1988 PCT Pub. No. WO88/10254 PCT Pub. Date Dec. 29, 1988.The invention is concerned with novel compounds of the formula <IMAGE> I wherein R1, R2, R3, R4, R5 and R6 have the significances given in the description, as well as enol ethers and salts thereof and their manufacture, weed control compositions which contain such compounds as active substances and the use of the active substances or compositions for the control of weeds. The invention is also concerned with certain starting materials which have herbicidal activity and with weed control compositions containing these.

Description

[Detailed description of the invention] heterocyclic compound The present invention relates to heterocyclic compounds, that is, general formula: R1 is hydrogen, C1-4 alkyl, C31* is a-alkenyl, C31t&! 4Al quinyl, or 01-4 haloalkyl, R2 is a group a or when Hl means haloalkyl, hydrogen, 01- 8 alkyl, 02-8 alkenyl, C2-8 alkynyl or C2-8 alkoxy means sialkyl; R3 is halogen 1 means cyano, R4 is hydrogen 1 means halogen, R5 means hydrogen, fluorine or 01-4 alkyl, R6 means 01-4 alkyl 1 liter means cl+4 haloalkyl, The symbols H7 each independently represent hydrogen 1fc means C1-3 alkyl, and n means 0.1 or 2, and Q is a saturated 3- to 7-membered carbocyclic ring; Q is a heterocyclic residue (which may optionally contain one or more 0 may be substituted with 1 to 4 alkyl groups), but in this case, the heterocyclic residue The group is one selected from oxygen and sulfur! fc has two heteroatoms, and may optionally have a keto functionality within the ring, or Q means a phenyl group, and this phenyl group is in some cases a yoshihalogen NC1- 4 alkyl, C1-4 haloalkyl, 01-4 alkoxy, 01-4 alkylthi Even if monosubstituted or polysubstituted by nitro, nitro, and/or cyano Often, and furthermore, a fused saturated carbocyclic ring can include a 5- to 7-membered heterocyclic ring. and this heterocycle has one or two oxygen atoms in the ring. and 6-aryluracil compounds of the formula l (wherein R1 is hydrogen or C1- 4 haloalkyl) as well as the corresponding enol ethers of compounds of formula l ( In the formula, R"E" refers to a salt of the compound in which R2 represents hydrogen.

Therefore, the enol ether has the formula: (wherein R3, R4, R5, R6, R7 , n and Q have the above meanings, R1' is 01-4 alkyl, and C33 is. a" Compounds having "Nyl, 1fc means C3, or alkyl" are included. It will be.

The compounds according to the invention have herbicidal action and are suitable as active substances in weed control compositions. There is. Therefore, the present invention provides a method for controlling weeds containing the compound according to the present invention as an active substance. Compositions, methods of making these compounds, and compounds or compositions that are companions for weed control. It also includes how things are used.

"Halogen" in Formula I above includes fluorine, chlorine, bromine and iodine. Al Kyl, alkenyl and alkynyl groups may be straight or branched and in this case also applies to the alkyl part of haloalkyl, alkoxy and alkylthio groups. do. A haloalkyl group can contain one or more halogen atoms (different from the same group). .

Examples of residues Q include dichloropropyl, cyclobutyl, cyclopene. Chil, cyclohexyl, cyclohebutyl, 2-oxiranyl, 2-methyl-2- oxiranyl, 6-oxetanyl, 3-methyl-3-oxetanyl, 3-ethyl -3-oxetanyl, 2-tetrahydrofuryl, 6-tetrahydrofuryl, 2- Tetrahydrogyranyl, 6-tetrahydropyranyl, 4-tetrahydropyranyl , 3-methyl-3-cetanyl, 6-titrahydrothienyl, 1,3-dioxy Ran-5-yl, 1,3-dioxan-5-yl, 1-oxo-4-tetrahydride lotiopyranyl, phenyl, 1,3-benzodioxol-5-yl, and 1 ゜6-Benzodioxan-6-yl.

Salts of compounds of formula I are especially alkali metal salts, such as sodium and potassium salts: Alkaline earth metal salts, such as calcium and magnesium salts: ammonium salts , that is, unsubstituted ammonium salt and monosubstituted 17'c are polysubstituted ammonium salts, For example, triethylammonium and methylammonium salts, as well as other organic Salt with a base such as pyridine.

The presence of at least one asymmetric carbon atom in a compound of formula I means that the compound is optically It exists in isomeric form and means scales. When an aliphatic C-C double bond exists, how many Many different sexes can occur. Formula I encompasses all of these possible isomeric forms as well as mixtures thereof. shall be included.

One interesting group of compounds according to the invention is where 11 is hydrogen, Cel4alkyl, C 317tG! 4 alkenyl,’! 7’ (is C3’Eik’!, meaning alkynyl) Consisting of compounds of formula l and the enol ethers and salts of these compounds to taste .

Another interesting group of compounds according to the invention are those in which R1 represents C-4 haloalkyl. R2 is hydrogen, C1-8 alkyl, C2-8 alkenyl, C2-8 fulky formula meaning nyl, 02-8-alkynylkyl or the group -(CR'R')n-Q from the compounds of l and salts of these compounds, and this Q is from the 5f03 member means a 7-membered carbocyclic ring or a heterocyclic residue, and the group has one or more C1-4 alkyl The heterocyclic group may be optionally substituted with residues selected from oxygen or sulfur within the ring. or Q means a phenyl group, and The levers are halogen, C1-4 alkyl, C-4 haloalkyl, C-4 a Rukoxy, C-4 alkylthio, nitro and (primarily) cyano optionally mono Substituted or polysubstituted.

If R1 is 03!7t, it is alkenyl or C3'! fc means alkynyl If so, this group is preferably allyl or propargyl. R6 is haloa If it means trifluoromethyl, this preferably means trifluoromethyl 1fc. Tafluoroethyl is good. In general, any halogen atoms that may be present are Fluorine, chlorine or bromine are preferable.

R1 is independent of each other (straight chain cl+4 alkyl, methyl, means 00-4 fluoroalkyl, and difluoromethyl, and R3 is Preferably, one element of chlorine means bromine, and R4 means hydrogen or fluorine. Gayo<, R5 preferably means hydrogen, fluorine or methyl, and R6 Narube (C □ ~ 4 el 4 alkyl means methyl (, each R7 is Naru) Preferably, it means hydrogen, and n preferably means O or 1.

A particularly suitable compound of formula l is 2-chloro-5-(3°6-cyhydro-2,6-cyhydro Oxo-6-methyl-4-trifluoromethyl-1(2)()-pyrimidinylz -Cycloheptyl, 6-tetrahydrofuryl, 1,3-4-fluorobenzoic acid Dioxan-5-yl, cycloprogylmethyl, tetrahydrofurfuryl, 1, 3-dioxolan-4-ylmethyl, benzyl, 4,4-dimethyl-2-oxo -tetrahydrofuran-3-yl, cyclopentyl, 1-cyclopropylethyl Oyohi cyclohexyl ester theal.

Yet another representative example of the compound represented by formula 1 is 2-chloro-5-[3,6-shihyu Draw 2.6-thioxo-3-methyl-4-trifluoromethyl-1(2H)- 6-nitrobenzyl, α,α-dimethylene (pyrimidinyl)-4-fluorobenzoic acid rubenzyl, tetrahydrothio7en-3-yl, 4-cyanophenyl and 3 ．． 5-ji()! J fluoromethyl)benzyl ester and 2-chloro-5- [3,6-dihydro3゜4-dimethyl-2,6-dioxy-1(2H)-pyri Cycloprogylmethyl of midinyl-4-fluorobenzoic acid, 1-cyclopropylene ruethyl, cyclopentyl, cyclohexyl, cycloheptyl, 3-tetrahydride Lofuryl, 1,6-thioxan-5-yl, 1,3-dioxolan-4-ylme Al with tyl, benzyl and tetrahydrofurfuryl esters.

Particularly suitable compounds of formula l in which R1 means cl+4 haloalkyl include: be: Improgyl 2-chloro-5-(3-difluoromethyl-6,6-sihydro 4-Methyl-2,6-dioxo-1(2H)-girimisonyl]-4-fluoropene nzoate, 2-chloro-5-[3-difluoromethyl-6,6-dihydro-4-methyl-2 ,6-dioxo-1(2H)-pyrimidinyl)-4-fluorobenzoic acid, Imp. Lopyl 5-[4-ethyl-3-difluoromethyl-3,6-dihydro 2.6 -dioxo 1(2H)-girimisonyl]-2-chloro-4-fluorobenzoe tort, Isopropyl 5-C4-ethyl-6-cyfluoromethyl-3,6-cyhydro 2,6-Dioxo 1(2H)-1smisonyl]-2-promo 4-fluorobe nzoate, Isopropyl 2-promo 5-(3-difluoromethyl-3,6-sihydro 4-Methyl-2,6-dioxy-1(2H)-pyrimidinyl-4-fluorobe nzoate, 2-proginyl 2-chloro-5-[6-cyfluoromethyl-6,6-cyhydro -4-methyl-2,6-dioxo-1(2H)-pyrimidinyl-4-fluoro benzoate, and Methyl 2-chloro-5-[3-difluoromethyl-6,6-dihydro-4-methyl Chill-2,6-dioxo 1 (2H)! 'Rimimisol: 1-4-fluorobenzo Eight.

Yet another representative example of such a compound of formula l is 2-chloro-5-(3 -difluoromethyl-6゜6-dihydro-4-methyl-2,6-dioxo 1( 2H)-pyrimidinyl-ethyl-4-fluorobenzoic acid, n-7' lobil, n -7'thyl, n-hexyl, n-octyl, 5ec-butyl, 1-methylbutyl , neopentyl, isobutyl, impentyl, 2-methylbutyl, 1,2-dimethyl Tylprogyl, tert-butyl, 1-ethylpropyl, allyl, 2-butenyl , 3-methyl-2-butenyl, 3-methyl-6-futhynyl, 1-ethyl-2-7 'lopenyl, 4-pentenyl, 1-/thi-2-7'tenyl, 1-methyl-3- butenyl, 3-phthynyl, 2-mef-2-7'ropenyl, 3-7''tenyl, 2 -butenyl, methoxymethyl, ethoxymethyl, n-propoxymethyl, iso Propoxymethyl, n-pentyloxymethyl, 1-methoxyethyl, 2-meth xyethyl, 2-ethoxyethyl, 2-isopropoxyether, 2-methoxy- 1-methylethyl, 2-n-butyloxyethyl, cyclopentyl, cyclohexyl sil, cycloheptyl, cyclopropylmethyl, 1-cyclopropylethyl, 3 -tetrahydrofuryl, tetrahydrofurfuryl, 1,3-dioxane-5-y 1,3-dioxiran-5-ylmethyl, benzyl and 4-methoxyphene Nyl ester, Improgyl 2-chloro-5-(3-difluoromethyl-6゜ 6-dihydro-4,5-dimethyl-2,6-dioxo-1(2H)-f rimisoni ]-4-fluorobenzoate, isopropyl 2-chloro-5-[3-Schiff k, tOmef k-3, (5-dihydro-5-fluoro-4-methyl-2 , 6-dioxy-1(2H)-pyrimidinyl-4-fluorobenzoate, Ramprogyl 2-chloro-5-[3-difluoromethyl-3,6-sihydro-4- Methyl-2,6-dioxo 1 [2H)-pyrimidinyl to benzoate and and isopropyl 2-chloro-5-(3,6-sihydro-4-methyl-3-(1, 1,2,2-tetrafluoroethyl]-2,6-dioxo 1(2H)-pyrimi Dinyl-4-fluorobenzoate.

9 for producing compounds of formula I and their enol ethers and salts The characteristics of the method according to the present invention are as follows: (a) Compounds of formula l in which R1 means hydrogen and optionally these compounds To produce metal salts, the general formula: 1B means lower alkyl, preferably C1-4 alkyl. ] is cyclized under basic conditions, and if necessary, the resulting compound of formula l is cyclized. Converting a metal salt of a uracil derivative to its acid form (Hl-hydrogen) by acid treatment, (b) R1 is C1-4 alkyl, 031fc+alkenyl, 0317'jc 4 fulkynyl or 01-4 haloalkyl, and 11 is cl+4 ha When meaning loalkyl, 12 is different from hydrogen to produce a compound of formula l. For this, the general formula: (wherein R2, R3, R4, R5 and R6 have the above meanings) The conductor is C1-4 alkyl, C3'f7'C is alkenyl, or C3'! *&! . For alkylation with a corresponding alkylating agent containing an alkynyl group In the preparation of compounds of formula 1 in which R1 is cl+4 haloalkyl, in formula 1' provided that R2 is different from hydrogen, (, /→ Compounds of formula l in which R1 is different from hydrogen and the corresponding enol ethers In order to produce the general formula: (wherein R3, R4, R5 and R6 are as defined above) It has a taste, R1" is C1-4 alkyl, c,, iyc is alkenyl, C31 benzoic acid having fc + alkynyl 1 liter means C1-4 haloalkyl) or its corresponding enol ether (in this case benzoic acid 1fc is the enol The ether may be present in the form of a reactive derivative) with the general formula 8% (In the formula, R2 has the above meaning, but tomodashi R1 means cl+4 haloalkyl. In the case of producing a compound of the formula (2), R2 in the formula (2) must be different from hydrogen. Hydroxy compounds of Stealized, ) In order to produce a compound of formula l in which R1 is different from hydrogen, the general formula: (In the formula, R1", R3, R', R5 and R6 have the above meanings, R9 is 01 ~6 alkyl, C2-4 alkenyl, C2-4 alkynyl or C2-6 alco The benzoic acid ester of the xyalkyl compound is converted into a hydroxy compound of formula (reagent ■ is higher than alkanol, alknol, or alkynol R80H) with a boiling point), or (E) Formula l in which R1 means C□~4 haloalkyl, and R2 means hydrogen In order to produce the compound, the general formula (In the formula, R3, R4, R5 and R6 have the above-mentioned meanings, and R1 is Cel4halo alkyl, and R2' has the meaning of R2 excluding hydrogen). Hydrolyzing the stell to the corresponding benzoic acid, (c) In order to produce the enol ether of the compound of formula I, the general formula (In the formula, R3, R4, R5, R6, R7, n and Q have the above meanings, Ha l means chlorine or bromine) in the presence of an organic base. Treat with alkanol, alknol or alkynol R”OH or Rui is a general formula %formula% (wherein R1' has the above meaning and Mo means an equivalent metal ion) The corresponding alcolade, alkanol iyc is treated with alkynolad and the necessary If necessary, the formula 1 obtained in this way (in the formula, R1 or R2 means hydrogen) ) is converted into a salt.

The cyclization described in variant (a) involves the cyclization of the compound of formula ] in an inert protic organic solvent, e.g. Alcohols, such as methanol, ethanol'! ! or improvisation tool; inactive aprotic organic solvents, such as aliphatic or cyclic ethers, such as 1.2- Dimethoxyethane, tetrahydrochloride/dioxane, or aromatic compounds , for example benzene′! ! or toluene: an inert aprotic radial solvent, e.g. dimethylformamide or dimethyl sulfoxide (such solvents are hydrocarbon , e.g. n-hexane 1fc can optionally be used as a two-phase mixture with toluene. ); or in water at a temperature from -78°C to the reflux temperature of the reaction mixture 1 This is conveniently carried out by treatment with a base. Sodium alcohol as base lard, alkali metal hydroxides, especially sodium hydroxide and potassium hydroxide alkali metal carbonates, particularly sodium carbonate and potassium carbonate, and It is preferable to consider sodium hydride. Using alkanol as a solvent If the solvent is 0. - (CR'R') Knee○ HK: It is convenient to match, and it also prevents undesirable beauty treatments from occurring at the same time. Le exchange reactions are avoided. When using sodium hydride as the base, the solvent is Preferably an aliphatic ether or a cyclic ether, dimethylformamide 1fc is dimethyl Rusulfoxide is good, and any of these solvents as a mixture with toluene May be used.

If one of the above bases is used, the cyclization will be completed and the resulting product will be is present in the form of the corresponding alkali metal salt. Isolate and purify this using known methods. or by acidifying the mixture to isolate each compound of formula I itself. Good too. Mineral acids such as hydrochloric acid or strong organic acids such as acetic acid or Preference is given to using p-toluenesulfonic acid.

The term "alkylation" in modified method (b) refers to the hydrogen atom of one N1 atom of the uracil nucleus. The child is C1-4 alkyl, Cs1fC.

Alkenyl, C3’! fcha4alkynyl'i7chacl~4haloalkyl group represents replacement with . C1-4 alkyl, C5Ef4 ha as an alkylating agent , alkenyl 1fc is Cs 1 fc c. Alkynyl halides, and) Each chloride 17t is bromide, sulfate, or multiple halogenation. cl-, alkanes such as chlorodifluoromethane, or monohalogenated or or multiple halogenated alkenes, such as tetrafluoroethene. It is.

This alkylation is carried out using an inert protic organic solvent, such as a lower alkanol, e.g. ethanol (optionally used in a mixture with water), an inert aprotic organic solvent, For example aliphatic ethers or cyclic ethers, such as 1,2-dimethoxyethane, Tetrahydrofuran or dioxane, ketones such as acetone and 2-butane Non- or inert aprotic polar organic solvents, such as dimethylformamide , dimethyl sulfoxide! fc in the presence of acetonitrile and a base, e.g. (hydrogenated) IJium, alkali metal hydroxide, sodium hydroxide 1 fc is potassium hydroxide, alkali metal alcolade, and toshiage sodium alcolade Lard, or alkali metal carbonate, is bicarbonate, also known as sodium carbonate. um, potassium carbonate, and sodium bicarbonate and the friend is 0°C in the presence of potassium bicarbonate The reflux temperature of the reaction mixture is conveniently carried out at room temperature, but the N1 atom When replacing a hydrogen atom with a C1-4 haloalkyl group, the temperature is preferably 50°C. It is preferable to carry out the process at a temperature of 100°C. To give one particularly suitable example, Equation 1 ’ is first treated with a base such as sodium hydride or sodium chloride in a solvent. Tanolade primary was treated with sodium carbonate and after a short reaction time halogenated in the same solvent. Treat with genide. In another embodiment, the uracil derivative 1' is dissolved in a solvent (e.g. Alkali metal bicarbonate in acetone), diluted with bicarbonate) is reacted with dialkyl sulfate in the presence of potassium bicarbonate at reflux temperature. child Depending on the solvent used, the reaction generally takes place in a relatively short time or a few hours. Sometimes it ends after a while.

Modified method (/ is a method in which the primary benzoic acid is an enol ether or a reactive derivative thereof) Esterification, which can be carried out according to known methods. For example, For example, 1 liter of benzoic acid of formula m is mixed with its corresponding enol ether salt in an inert diluent. at a temperature of medium room temperature to 100°C, e.g. at the reflux temperature of the reaction mixture, preferably at 40°C. In the temperature range from °C to 70 °C, halides and is iodide or sulfate of hydroxy compound, mesylate), 17t is reacted with tosylate. of benzoic acid of formula m or the corresponding enol ether As salts, in particular alkali metal salts, such as sodium, potassium or lithium salts of alkaline earth metals, such as magnesium, calcium or barium salts , and organic bases such as tertiary amines such as triethylamine, 1,5-silane Adebicyclo(4,3,0)-5-nonene, 1,8-thiadebicyclo(5, 4,01-7-undecene and 1°4-thiadebicyclo(2,2,2)oc Salts with tan are considered, but alkali metal salts, sodium salts and potassium salts are also considered. Um salt is good. Diluents that can be used are preferably inert organic solvents, such as lower alkaline solvents. Canols, e.g. ethanol, aliphatic ethers and cyclic ethers, e.g. Tyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxa ketones, such as acetone and 2-butanone, dimethylformamide, dimethylformamide, Methyl sulfoxide, acetonitrile and hexamethyl phosphoric triamide are stomach. Salt is a suitable inorganic base, such as an alkali metal! fc is alkaline earth metal carbonate The first salt is the reaction of a bicarbonate, hydroxide or hydride, or an organic base with an acid. The salt can be recovered in situ by obtaining the salt, which can then be added to the same reaction medium. react with a second reactant in a medium.

Reactive acid halide of benzoic acid or its corresponding enol ether When used as a derivative, it can be dissolved in an inert organic solvent such as an aliphatic ether or is a cyclic ether, such as diethyl ether, 1,2-dimethoxyethane, tetra hydrofuran or dioxane, aliphatic or aromatic hydrocarbons such as n-hexane San, benzene and toluene, or hydrogenated hydrocarbons, and chlorine. carbonized hydrocarbons, such as methylene chloride, chloroform, TFC is carbon tetrachloride width of about -2 Hydroxyl of formula It is convenient to react with a compound. Furthermore, in the first order, this reaction is performed using an acid binder, e.g. For example, organic bases such as triethylamine, glysine, 1,5-thiadebicyclo( 4,3,0)-5-nonene, 1,8-diadebicyclo(5,4,0)-7-u Ndecene 1 friend is convenient in the presence of 1,4-thiadevicycloC2,2,2]octane It can be implemented. This acid halide is preferably an acid chloride.

Further reactive derivatives of benzoic acid or the corresponding enol ether of formula m , the corresponding 0-acyl-1,3-dicyclohexylisourea and the corresponding Examples include N-acylimidazole or acid anhydrides. Such derivatives are Similarly to the halide, proceed with the reaction to the desired benzoic acid ester. It can be reacted with Roxy compounds. However, in these cases, the use of acid binders use is unnecessary.

In a variant, the reaction described in ) involves the hydroxylation of an excess of the benzoic acid ester of formula V to the hydroxyl of formula II. reaction mixture, preferably in the presence of a basic catalyst, e.g. sodium cyanide. This can be conveniently carried out by heating the substance to its reflux temperature.

During the course of the reaction, the residue R9 of the benzoic acid ester (2) becomes the R2 group of the hydroxy compound (2) di-substituted, so that low-boiling alkanols, alknols or alkyl NorR'OH is liberated.

Hydrolysis of the benzoic acid ester l" described in modified method ((e)) is carried out by a known method. Particularly strong mineral dispersions, such as sulfuric acid or bases, such as alkali metals and alkaline earths. Using a metal aqueous dispersion, for example, sodium hydroxide 19 is potassium hydroxide, 1 fc Optionally an organic solvent, such as an alcohol, such as methanol or ethanol, or in the presence of chlorinated hydrocarbons, e.g. methylene chloride, and optionally mixed with water. It can be carried out by using it as a compound.

Hydrolysis is conveniently carried out at temperatures between -20°C and 100°C, preferably at room temperature. Ru. If the product is present as a salt after alkaline hydrolysis, this can be e.g. It can be isolated by evaporating the solvent. The free acid then converts the salt into an acid, preferably or by acidification with mineral acids such as hydrochloric acid or sulfuric acid.

The term "metal ion" in variant (c) refers in particular to alkali metal ions, e.g. Thorium 1fc is a potassium ion or an alkaline earth metal ion, e.g. Represents lucium or magnesium ion. Sodium ions are particularly suitable It's on. Using alkanol, alknol or alkynol R”OH Gylysine is a particularly suitable organic base.

The reaction was carried out in an excess of the corresponding alcohol 1/○H as a diluent at temperatures between 0°C and 50°C. It is convenient to carry out the process at room temperature, preferably at room temperature.

The desired salt of the compound [manufactured directly by the above chlorination reaction under basic conditions] is , in a known manner, e.g. in solution of the respective inorganic or organic base. Compounds can be prepared from these compounds by melting. This salt-shaped bottom is generally It is done in a short time at a warm temperature. To give one specific example, an equivalent amount of uracil induction Disperse uracil derivative l in water using sodium hydroxide and sodium hydroxide) The disodium salt is formed by dissolving it in solution at room temperature. Then suitable inert The solid salt can be isolated by precipitation with a solvent or by evaporation of the solvent. One more thing One specific example is to prepare an aqueous solution of an alkali metal salt of a uracil derivative l with an alkali metal salt. Avoid introducing into aqueous solutions of salts containing metal ions other than ions; A second metal salt of the uracil derivative is prepared. This specific example is generally water-insoluble. Useful in the production of uracil metal salts.

The resulting compounds of formula I, enol ethers and alkaline compounds can be prepared in a simple manner according to known methods. Can be separated and purified. Furthermore, possible combinations of variants (b) to (c) can occur simultaneously. A convenient sequence of operations to avoid possible undesirable reactions is within the skill of those skilled in the art. By the way.

Unless a synthesis is specifically designed to isolate the pure isomer, the product will be Occurs as a mixture of two or more isomers. These isomers are separated using known methods. can. If necessary, pure optically active isomers can be obtained, e.g. from the corresponding optically active starting material. It can be manufactured by synthesis from raw materials.

The starting material of formula 1 is novel and can be prepared by known methods, e.g. in the following reaction steps. It can be produced according to the scheme [methods aa), bb) and CC)].

Reaction scheme ■　■ In the above reaction scheme, R3, R4, R5, R6, R7, R8, n and Q are R5' means hydrogen or 01-4 alkyl, R6' means cl+ -4 alkyl, and HIO means lower alkyl, preferably C0-4 alkyl. means kill.

To carry out process aa), compounds of formulas ■ and ■ are dissolved in an acidic diluent in an essentially anhydrous diluent. It is convenient to react with each other at elevated temperatures in the presence of a catalyst. Toshiba is used as a diluent. Organic solvents that form azeotropes with water, such as aromatic compounds, such as benzene , toluene, and xylenes, halogenated hydrocarbons such as methylene chloride, loloform, carbon tetrachloride and chlorobenzene, and aliphatic ethers and rings ethers such as 1,2-dimethoxyethane, tetrahydrofuran and Considering that xane, 'E7 can be used as an acidic catalyst. and hydrochloric acid, organic acids such as p-)luenesulfonic acid, phosphoric acids such as orthophosphoric acid and and acidic cation exchangers, such as rAmt)er1 7st 15 J (Fluka) is being considered.

The reaction is generally carried out at a temperature in the range of about 70°C to 120°C, preferably at a temperature of about 70°C to 120°C. Perform at reflux temperature. Under these reaction conditions, rapid removal of the water produced in the reaction was achieved. Ru.

The reaction according to method bb) is carried out in an essentially anhydrous aprotic organic solvent, such as an aliphatic Ethers or cyclic ethers, such as diethyl ether, 1,2-dimethoxye tane, tetrahydrofuran, or dioxane, aliphatic or aromatic hydrocarbons, For example n-hexane, benzene, toluene or xylene, or halogenated Aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride or 1.2 - in the presence of dichloroethane and optionally a base, especially an organic quaternary base, e.g. triethylamine or pyridine (the latter acts not only as a solvent but also as a base) or metal hydrides, such as IJium or potassium hydride Conveniently performed in the presence of The reaction temperature is preferably about -80°C to 50°C. It is preferable to carry out the reaction at a temperature within this range, and in particular, it is preferable to carry out the reaction at a temperature from -30°G to room temperature.

The reaction according to method cc) is carried out in a water-miscible inert organic solvent, such as an aliphatic ether. 1fc is a cyclic ether, such as 1,2-dimethoxyethane, tetrahydrofuran 1fc is dioxane or a lower alkanol such as ethanol at 50°C. to 100°C, preferably at reflux of the reaction mixture, or at a temperature of 100°C. Acidic catalysts such as hydrochloric acid or is 50°C to 100°C, preferably 60°C in the presence of p-) luenesulfonic acid. It is convenient to carry out the reaction at a temperature of 80°C.

The starting materials of formulas m and ■ and their preparation are mostly described in European Patent No. 195,346 It is stated in the specification of the No.

Starting materials m and V for which no manufacturing method is described can be made in the same manner as known starting materials. I can do it. Reactive derivatives of benzoic acid of formula m which can also be used as starting materials are can be prepared from these benzoic acids according to known methods. On the other hand, benzoic acid m all enol ethers, i.e. the general formula Compounds of can also be used as starting materials in variant (c), and these are new and be. These can be used, for example, in the following reaction scheme (where R3, R4, R5, R6, R 1', R', Hal and M■ have the above meanings).

Reaction scheme IV a When halogenating benzoic acid ester of formula Xm, wrinkles are used as a halogenating agent. Thionyl chloride, phosphorus pentachloride or phosphorus oxychloride or phosphorus pentabromide It is bromide Phosphoryl is used. If necessary, a mixture of phosphorus pentachloride and phosphorus oxychloride may be used. Alternatively, a mixture of phosphorus pentabromide and phosphoryl bromide is used; phosphorus oxychloride or phosphoryl bromide can serve as diluents. Chlorinated or Brominated is an inert diluent, especially an aprotic organic solvent, e.g. aliphatic 1fc is an aromatic Aromatic hydrocarbons, such as n-hexane, benzene, toluene, or xylene, rogenated aliphatic hydrocarbons, such as methylene chloride, chloroform or 1,2-di Chloroethane, a halogenated aromatic hydrocarbon, e.g. chlorobenzene,’ifc It can be carried out in the presence of a 6th amine such as N,N-dimethylanili/but If phosphorus sichloride or phosphoryl bromide is used as the halogenating agent, this Not necessarily necessary. When using thionyl chloride as a halogenating agent, It has been found convenient to add a medium amount of dimethylformamide. The reaction temperature is Generally from 0’C to the reflux temperature of the reaction mixture, preferably from 80°C to 120°C It is.

The reaction between compound XIV and compound (2) can also be carried out in the same manner as in the modified method (c).

The subsequent hydrolysis of compound xV is carried out according to known methods, inter alia using inorganic acids. and optionally in the presence of an organic solvent and/or water. As an acid, It is preferable to use hydrochloric acid, sulfuric acid, and phosphoric acid, and alcohol as an organic solvent. Examples include ethanol, aliphatic ethers 1 include cyclic ethers, such as 1,2-di Methoxyethane, tetrahydrofuran and dioxane, ′! Optionally chlorinated fat Aliphatic or alicyclic hydrocarbons, such as methylene chloride, tetrachloromethane, n-h Preference is given to using xane and cyclohexane. The reaction temperature is generally -20°C. From 120°C1 preferably from 0°C to 30°C1 and from 15°C to 20°C. be.

Reactive derivatives of enol ethers of benzoic acid m (which can also be used as starting materials) can be produced from enol ethers according to known methods.

The starting material of formula (2) used in the modified method (f) is prepared in the same manner as in the above method Xln→Xrv. , can be produced by halogenating the corresponding uracil derivative of the above formula l' (See reaction scheme and subsequent description of reaction conditions).

/Variation (→” and ((e)) Uracil of formula 9 l′ and l” serves as the primary starting material Derivatives are a subgroup of compounds of formula l. Variants (c), ni), and (g) and The starting materials and reagents for the remainder included in the reaction scheme are known or can be prepared using known methods. It can be manufactured according to the law.

Compounds of formula I as well as their enol ether primary salts have herbicidal properties and many cultivated plants of various cultivated crops, especially grains, soybeans, corn, rice, and cotton; The weeds in the middle of the day, 5etaria faberii.

Digitalia sanguinalis, Poa annua, C henopodium-album, Amaranthus retrof lexus, abutilontheophrasti, 5inaps Suitable for controlling is alba and Daturastramonium . Furthermore, these compounds are not only pre-emergent herbicides, but also post-emergent herbicides. be.

The compound of formula 1na and their salts also have herbicidal properties and, like compound 1, kill weeds. , and can be used to control the pests listed above. Novel compound 11a and its salts thereof, weed control compositions containing these compounds as active substances, A previously defined method of producing the compound and a method of controlling weeds. The use of the compound 1fc in the composition further forms an object of the present invention. Compound ma Salts include Toshiwage alkali metal salts, alkaline earth metal salts, ammonium salts and Related to Compound I are the salts with organic bases mentioned above in detail. The compound lea is It can be converted into a salt in exactly the same way as compound 1. Below, compounds of formula l and their eno According to the invention, compounds and their salts of the formula lea as well as ethers or salts of We shall refer to such compounds collectively.

In practice, from 1 g of the compound according to the invention to 3 hectares, preferably according to the invention. 10 to 500 S/ha of compound is usually sufficient to achieve the desired herbicidal effect. Ru. A concentration range of 15 to 100 g/ha of the compounds according to the invention is particularly preferred. stomach.

A feature of the weed control composition according to the invention is that it contains an effective amount of the previously defined formula IC. ), or an enol ether or salt thereof, or The composition contains a compound of formula 1(a) or a salt thereof and a formulation auxiliary. this The composition may contain at least one of the following formulation aids, solid carrier materials, solvents or dispersion media. surfactants (wetting agents and emulsifiers), dispersants (those without surfactant action) ), and stabilizers. Using these and other adjuvants These compounds and herbicidal active substances are prepared using conventional preparations, such as dusts and powders. , can be converted into granules, solutions, emulsions, emulsifiable concentrates, pastes, etc.

Compounds of formula I, their enol ethers and compounds of formula Ia are generally insoluble in water. salts, especially alkali metal salts and ammonium salts, are generally Water-soluble or water-insoluble or water-soluble compounds with respective formulation aids It can be formulated according to methods useful for. The composition can be manufactured by known methods, e.g. For example, the specific active substance can be mixed with a solid carrier material and dissolved in a suitable solvent or dispersion medium. or suspending and, if necessary, wetting agents, emulsifying agents and/or dispersing agents. dilution of pre-prepared emulsifiable concentrates with solvents or dispersion media using surface-active substances; This can be done by

As solid support material, natural mineral substances such as chalk, dolomite, limestone, alkali can be used. mina and silicic acid and its salts (e.g., silicic acid, kaolin, bentonite, talc, attapulgite, and montmorillonite), synthetic mineral substances, altitude Dispersed in silicic acid, aluminum oxide and silicates, organic substances such as cellulose - starch, urea and synthetic resins, and fertilizers, such as phosphates and nitrates This carrier material can be added as a powder or as granules, for example. Wear.

Aromatic compounds such as benzene, toluene, xylene are used as solvents or dispersion media. and alkylnaphthalenes, chlorinated aromatic compounds and chlorinated aliphatic carbonization. Hydrogen, such as chlorobenzene, chloroethylene, hydrogen and methylene chloride, aliphatic carbons Hydrogenides, such as cyclohexane and puffins, such as petroleum distillates, alcohols such as butanols and glycols, and their ethers and esters. esters, ketones such as acetone, methyl ethyl ketone 1 methylinobutyl ketone ton and cyclohexanone, and strongly polar solvents or dispersion media such as dimethyl formamide, N-methylpyrrolidone and dimethyl sulfoxide and water. Essentially, such solvents preferably have a flash point of at least 30°C and a boiling point of at least 30°C. It is preferable to have a temperature of at least 50°C. So-called liquefied gas in the solvent or dispersion medium Sweater extenders or carrier materials are contemplated.

These are products that are gases at room temperature and under normal pressure. Examples of such products are Aerosol propellants, such as hydrogenated hydrocarbons such as dichlorodifluoromethane It is tan. If the weed control composition according to the present invention is provided in the form of a pressurized pack, In this case, it is convenient to include a solvent in addition to the propellant.

Surface-active substances (wetting agents and emulsifiers) are non-ionic compounds such as fatty acids, alcohol, or condensation products of fatty substituted phenols with ethylene oxide, sugars fatty acid esters and ethers of saccharides or polyhydric alcohols, product obtained from alcohol by condensation with ethylene oxide, ethylene oxy A block polymer of hydrogen and propylene oxide, or alkyldimethylamine Oxide is fine.

Surfactants are also anionic compounds, such as seracune, fatty sulfate esters, e.g. For example, sodium dodecyl fiate, sodium octadecyl sulfate, and cetyl sulfate. sodium, alkyl sulfonates, arylsulfonates, and fatty-aromatic aromatic sulfonates, such as alkylbenzene sulfonates, such as dobufulvene; calcium zenesulfonate, and butylnaphthalenesulfonate, and more Amides of complex fatty sulfonates, such as oleic acid and N-methyltaurine Condensation products and sodium sulfonate of dioctyl succinate may also be used.

Finally, surfactants include cationic compounds, such as alkyldimethylbenzyl acetate. ammonium chloride, sialyldimethylammonium chloride, alkyl trichloride With methylammonium chloride and ethoxylated quaternary ammonium chloride Good too.

Lignin and lignin sulfonic acid are used as dispersants (those without surfactant action). Sodium and ammonium salts of maleic anhydride-diisobutylene copolymerization sulfoylated polycondensate of sodium salts, naphthalene and formaldehyde The sodium and ammonium salts of the product, and the sodium and ammonium salts of the It is being

As a dispersing agent, which is particularly passed as a thickening agent or an anti-settling agent, e.g. Lulose, carboxylic methyl cellulose, hydroxyethyl cellulose, polyvinyl cellulose Nil alcohol, alyanate, caseinate and blood albumin are used. Ru.

Examples of suitable stabilizers are acid binders such as chlorohydrin, phenyl glycidium, etc. ethers and soybean compounds, antioxidants such as gallic acid esters and butylated hydroxytoluene, UV absorbers such as substituted benzophenones, diphenylene nyl acryloni) lJjs4 ester and cinnamic acid ester, and deactivating agent , for example salts of ethylenediaminotetraacetic acid and polyglycols.

The weed control composition according to the invention contains, in addition to the active substance according to the invention, synergists and other Contains active substances such as insecticides, acaricides, fungicides, plant growth regulators and fertilizers be able to. Such combination compositions may be used for enhanced action or for It is used to widen the spectrum.

Weed control compositions according to the invention generally contain one or more compounds according to the invention as active substances. It contains 95% by weight, preferably from 0.5 to 75% by weight, of compounds o, ooi.

These compositions are provided in a form suitable for storage and transportation. Such preparations, e.g. In emulsifiable concentrates, the active substance concentration is usually in the high range, preferably in the high range. ranges from 1 to 50% by weight, and between 10 and 30% by weight. Next, these preparations are The active substance concentration diluted with a different inert substance and used in actual use, i.e. 10% by weight is obtained from approximately o, ooi, and 5% by weight is obtained from approximately 0.005. can be done. However, this active substance concentration may be lower or higher.

As mentioned above, the weed control composition according to the present invention can be produced by a known method.

For the production of pulverulent preparations, the active substance, i.e. at least one compound according to the invention, is used. can be mixed with a solid carrier material, e.g. by grinding together, or The carrier material is impregnated with a solution or suspension of the active substance and then the solvent or dispersion medium is reduced. Evaporation and heating under pressure! It can be removed by bamboo suction. surfactant or dispersant 6 additions make such powder formulations easily wettable with water, thus making them These can be converted into aqueous suspensions, passed for example as spray compositions.

Wettable powders also allow the active substance to be dispersed in water by mixing it with a surfactant and a solid carrier substance. or mixed with a granulated solid carrier material to form a granular product. You can also

If necessary, the active substance can be dissolved in a water-immiscible solvent, for example a high-boiling hydrocarbon (this is (conveniently containing a decomposed emulsifier), and the solution is then dissolved in water. It becomes self-emulsifying when added to. Alternatively, the active substance is mixed with an emulsifier After mixing, the material can then be diluted with water to reach the desired concentration. Furthermore, active substances may be dissolved in a solvent and then the solution mixed with an emulsifier. Such mixtures are also It can be diluted with water to achieve the desired concentration. This method produces emulsifiable concentrates or A ready-to-use emulsion is obtained.

The method of using the weed control composition according to the present invention constitutes a further object of the present invention. carried out according to the usual application methods, e.g. spreading, spraying, dusting, watering or dispersing. can. The weed control method according to the present invention can be applied to a place to be removed from weeds and/or Treating weeds with a compound according to the invention or a weed control composition according to the invention It is particularly characterized by

The following examples will more easily explain the invention.

■Type 0! Production of compounds: 2-Chloro-5-(3,6-hydro-2,6-thio-3-methyl-4-to) Lifluoromethyl-1(2H)-pyrimidinyl]-4-fluorobenzoic acid 3.0 9 in benzene 20- and thionyl chloride 2.91 nt. Heat both Mido and 2 at reflux temperature for 3 hours. The reaction mixture was then evaporated to dryness and dioxidized. Dissolve in Sun 20d. This solution is mainly composed of the acid chloride of benzoic acid and the solvent. It will be. This was combined with 0.861 3-cetanol and pyridine in 10 d of dioxane. Add to 1.0 g of solution. The reaction mixture was then stirred at room temperature for 2.5 hours and watered with 4 00- and extracted twice with ethyl acetate 4001 each time. combined organic The phase was chlorinated twice with 200 g of 1N hydrochloric acid each time and saturated with 2001117). Wash once with silica solution, dry over anhydrous sodium sulfate and evaporate. vinegar residue Chromatography on silica sol using ethyl acid/n-hydrochloride (2:3) Purify it. In this method, chetan-3-yl 2-chloro-5-(3,+5 -dihydro-2,6-cyone-3-methyl-4-trifluoromethyl-1(2 H)-biIJmisonyl)-4-fluorobenzoate is obtained, which is diluted with acetic acid. Can be recrystallized from ethyl/n-hexane. Melting point: 121-126°C.

Similarly, 2-chloro-5-(3,6-dihy)”a-2,6-cyoxy-3- Methyl-4-trifluoromethyl-1 (2H)-hilJ misonyl m1-4- Starting from fluorobenzoic acid, via its acid chloride, the following hydroxy compound When reacting with 4-fluorobenzoate, Using dicloheptator, cycloheptyl 2-chloro-5-(3,6-cycloheptyl Draw 2,6-thioxo-3-methyl-4-trifluoromethyl-1(2H)- Pyrimidinyl-4-fluorobenzoate is obtained as an oil. IH-NMR (D , -DMso, 400 M) (Z): 1.40-1.82 (m, 1 0H), 1.94-2.04 (m, 2H), 3-41 (1!.

3H), 5-07-5.16 (m11H), 6-61 (s, IH) , 7-87 (a, 1a), 8.00 (a, 1H): 3-hydroxytetrahyde Tetrahydrofuran-3-yl 2-chloro-5-(3, 6-sihydro-2,6-thioxo-3-methyl-4-trifluoromethyl-1 ( 2I()-pyrimidinyl-4-fluorobenzoate is obtained as an oil. IH- NMR (D6-DMSo, 400 MHz): 2.01-2.10 ( m, IH), 2.20-2.31 (m, IB), 3.42 (s ,3H),3.73-3-80(3-80(,3,82-3,91(m,3 H), 5.48-5.53 (msIH), 6.62 (sslH), 7.89 (d, 1), 8.07 (asl: [(); 5-hydroxy-1,3-di Using oxane, 1゜3-dioxan-5-yl 2-chloro-5-(3゜6 -Sihydro2,6-thioxo3-methyl-4-trifluoromethyl-1(2 H)-pyrimidinyl-4-fluorobenzoate is obtained as an oil. IH-N' MR (D6-Dlxso, 400 az): 3.42 (s, 3 H), 3.97-4.02 (m, 2H), 4.05-4.11 (m, 2H ), 4.78 (a.

IH), 4.88-4.93 (m, 2H), 6.62 (a, I H), 7.92 (ds IH), 8.08 (d, IH); cyclopropylene Cyclopropylmethyl 2-chloro-5-(3,(S- Dihydro-2゜6-cyoxy-3-methyl-4-trifluoromethyl-1 (2H ) l'lJ midinimiso-4-fluorobenzoate is obtained as an oil. IH-NM R (D6-DMSo, 4DOMHz): 0.34-0.39 (m, 2H) , 0.54-0.60 (m, 2H), 1.16-1.24 (mslH), 3 ．． 42 (s, 3H), 4.15 (D, 2H), 6.61 (s, lH), 7 ．． 90 (a, 1H), 8.05 (a, IH); 3-hydroginemethyl-3 -(6-Methyl-6-oxetanyl)methyl 2 using methyl-oxetane -chloro-5-(3,6-sihydro-2,6-thioxo-3-methyl-4-tri Fluoromethyl-1(2H)-pyrimidinyl-4-fluorobenzoate oil and get it. IH-NMR (D6-DMSo, 400 MHz): 1. 35Ce, 3H), 3.42 C8, 3H), 4.30 (a, 2H ), 4.44 (Sun, 2H), 4.48 (a, 2) (), 6.62 (θ, IH), 7.90 (a, IH), 8.07 (a, IH) 　; Using 2-tetrahydrofurylmethanol, tetrahydrofurfuryl 2-k rolo-5-(3,6-sihydro-2,6-thioxo-3-methyl-4-triflu Oromethyl-1(2H)-pyrimidinyl-4-fluorobenzoate as oil Just relax. IH-NMR (D, -DMSo, 40 QyHz): 1.5 9-1.70 (m s IH), 1-76-1.90 (m, 2H), 1. 93-2.04 (m, IH), 3.42 (s, 3H), 3-62-3.69 (m, ll1), 3-72-3-80 (!D, IH), 4.11- 4.17 (m, IH), 4.21-4.33 (m, 2H), 6.61 (s , IH), 7.90 (a% IH), 8.05 (a, IH): 4 Using -hydroxymethyl-1,3-dioxolane, (1,3-dioxolane -4-yl)methyl 2-chloro-5-(3,6-sihydro-2,6-thioxo -3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl-4-ph The fluorobenzoate is obtained as an oil. IH-NMR (D6-DMSO, 400M Hz): 3.42 (s, 3H), 3.67-3.72 (m, IH), 5.96-4.04 (m.

IH), 4.32-4.42 (m, 3H), 4.83 (e, I H), 4.94 (xlH), 6.62 (tl!, 1H), 7.91 (a, IH), 8.08 (d, 1H): Using benzyl alcohol, benzyl 2-chloro-5-[:3,6-cyhydro rho-2,6-thioxo-6-methyl-4-trifluoromethyl-1(2H)-pi Rimidinyl-4-fluorobenzoate is obtained as an oil. IH-NMp, ( D, -DMSO, 400MHz): 3.40 (e%3H), 5-3 7 (s-, 2H), 6.60 Cta X IH), 7.36-7-4 3 (m-3H), 7.47-7.50 (to, 2H), 7.90 (a, IH), 8-08 (dsIH); Using R-4,4-dimethyl-3-hydroxy-2-oxotetrahydrofuran 4,4-dimethyl-2-oxo-tetrahydrofuran-3-yl R-2- Chloro-5-C3,6-sihydro-2,6-thioxo-3-methyl-4-trif fluoromethyl-1(2H)-bilimisonyl]-4-fluorobenzoate with oil and get it. [α)Q0=-10,6°: lH-takeR(D6-DMsO240Q yHz): 1-11 (es3H), 1-22 (8%3H), 3-43 (a% 3H), 4.13 (11, IH), 4.24 (a, IH ), 5.89 (s.

-1H), 6.62 (a, IH), 7.96 (a, 1H), 8.15 (a, IH); 4-hydroxy'-2+2+6+6-titramethyl-tetrahydrothio Using biran, 2,2,6,6-titramethyl-tetrahydrothiopyran-4 -yl 2-chloro-5-(3,6-sihydro-2,6-thioxo-6-methyl -4-trifluoromethyl-1(2H)-pyrimidinyl]-4-fluoropenzo Get it by oiling the ethos. IH-NMp, (D6-D>Aso, 4 C1O MHz): 1.25 (s, 6H), 1.49 (8, 6H), 1.61 ( t, 2H), 2.19 (aa.

2H), 5-42 (s, 3H), 5.31-5.38 (m 11H) , 6.62 C811B), 7.89 (d, 1H), 8.06 (ds1H ) ; Using cyclopentanol, cyclomethyl 2-chloro-5-(3, 6-sihydro-2,6-thioxo-3-methyl-4-trifluoromethyl-1 ( 2H)-Birimisonyl]-4-fluorobenzoate is obtained as an oil. IH→% R (D6-DMso, 400 MHz): 1.50-2-DO (ms 8H), 3.42 ('53H), s31-5.38 (m.

IH), 6.61 (sslH), 7.87 (a, iH), 8.02 (as iH): Using phenol, phenyl 2-chloro o-5-[3,6-cyhydro Rho-2,6-thioxo-3-methyl-4-trifluoromethyl-1(2m()- Pyrimidinyl-4-fluorobenzoate is obtained as an oil.

IH-NMR (D6-nMso, 400 MHz): 3.43 (a , 3H), 6.63 (II, IH), 7.30-7.37 (m, 3H), 7.45-7.53 (m 12H), 7-99 (a-, IH ), 8-39 (''11H): Using 2-cyclohexylethanol, 2-Cyclohexylethyl 2-chloro-5-(3,6-cyhydro 2,6-cyhydro Oxy-3-methyl-4-trifluoromethyl-1(2H)-1? lJmidinyl ]-4-fluorobenzoate is obtained as an oil. IH-NMR (D6-DMSo .

40 QyHz’): 0.87-0.98 (m, 2I(), 1.10- 1.25 (m, 3H), 1.32-1.45 (m, IH), 1.56-1.7 5 (111% 7H), 3.42 (8% 3H), 4.34 (t, 2H), 6 ．． 61 (sslH), 7.89 (d, IH), 8.03 (cl, 1H); Using 1-cyclopropyl ethanol, 1-cyclopropyl ethyl 2-chloro-5-(3,6-sihydro-2,6-thioxo-6-methyl-4 -trifluoromethyl-1(2H)-16rimidinyl)-4-fluorobenzoe obtained as oil. lH-NMa (D6-DMSO.

400 MH2): 0.34-0.45 (rn, 2H), 0.47 -0.60 (m, 2H), 1.08-1.18 (m, IH), 1-38 (d s3H), 3.43 (ss3H), 4.55 (msIH), 6.61 (s , IH), 7.88 (d, IH), 8.01 (cl, IH), mass -Spectrum (m/e): M” 434 (4); Using p-methoxyphenyl, p-methoxyphenyl 2-chloro-5-(3 ,6-sihydro-2,6-cyoxy-3-methyl-4-trifluoromethyl-1 (2I()-biIJ misonyl m1-4-fluorobenzoate is obtained. Melting point 12 8-129℃. Mass spectrum (m/e) 2M”472 (24): Using 5-hydroxy-1,3-benzodioxool, 1,3-benzodioxol xol-5-yl 2-chloro-5-(3,6-sihydro-2,6-sioxo -3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-ph Obtain fluorobenzoate.

Melting point 134-135°C. Mass vector (rn/e): M”486 (1 5); 2. Using 4-dichlorobenzyl alcohol, 2゜4-dichlorobenzyl 2 -chloro-5-(3,6-sihydro-2,6-thioxo-3-methyl-4-tri Fluoromethyl-1(2H)-16rimidinyl]-4-fluorobenzoate obtain. Using 3-nitropenzyl alcohol with a melting point of 88-90°C, 3-nitro Lophenyl 2-chloro-5-(3,6-sihydro-2,6-thioxo-6-methyl Thiru-4-trifluoromethyl-1(2I()-pyrimidinyl)-4-fluoro Obtain benzoate. lH-NMR (D, -DMSo, 400MH2) :3.41 (s, 3H), 5.52 (e, 2H), 6.60 (a , 1! (), 7.70-7.74 (m% IH), 7.92 (6% IH), 7.95-7.98 (ro.

IH), 8.12 (d, IH), 8.20-8.26 (m, IH), 8.3 7-8.39 (rn, IH) Mass spectrum (m/e): M” 50 1(3)d Using diclohexanol, cyclohexyl 2-chloro-5-(3,6-cyclohexyl Hydro-2,6-thiokyso-3-methyl-4-trifluoromethyl-1 (2H )-pyrimidinylcy 4-fluorobenzoate is obtained.

IH-NMR (Do-DM30, 400MH2): 1.27-1.59 (m)

6H), 1.66-1.76 (m, 2H), 1.86-1.96 (m, 2H) , 3.39 (8,31H), 4.93-5-00 (m% IH), 6- 61 (s, IH), 7.87 (a, IH), 8.01 (a, IH); Mass spectrum (m/e): M" 448 (1); 3.5 -3.5-bis(trifluoromethyl)benzyl alcohol Litrifluoromethyl)phenyl 2-chloro-5-(3,6-sihydro2, 6-thioxo-3-methyl-4-trifluoromethyl-1(2H)l'rimimiso ]-4-fluorobenzoate is obtained. Melting point: 129-130°C.

Using p-cyanophenol, p-cyanophenyl 2-chloro-5-(3,6 -Shihydro2,6-thioxo3-methyl-4-trifluoromethyl-1(2 H')-pyrimidinyl)-4-fluorobenzoate is obtained. IH-NMR (D o-DMSo, 400 MH2): 3.43 (s, 3H), 6.63 ( s, IH), 7.57-7.61 (m, 2H), 7.98-8.02 (m, 3H), 8.42 (aia): using tetrahydrothiophene-3-ol Tetrahytrothien-3-yl 2-chloro-5-(3゜6-sihydro2 ．． 6-thioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine Nilcy 4-fluorobenzoate is obtained. II(-NMR(Do-DMSo) , 400MH2): 1.98-2.09 (m11H), 2.28-2. 38 (m, IH), 2.91-3-DO (m, 3H), 3.18-3.24 (rn s IH), 3.42 (s N 3H), 5.66-5.73 (rn, IH), 6.62 (s, IH), 7.89 (aslH), 8.0 3 (a, 1H); Using tetrahydrobilan-4-ol, tetrahydro Pyran-3-yl 2-chloro-5-(3,6-sihydro-2,6-thioxo 3-Methyl-4-trifluoromethyl-1(2H)-pyrimidinyl)-4-fluor Obtain orobenzoate. Melt Al 73-174°C.

2. Using 2-dimethyl-4-hydroxymethyl-1,3-diofuran, ( 2,2-dimethyl-1,3-dioxolan-4-yl)methyl 2-chloro-5 -(3,6-sihydro-2,6-thioxo-3-methyl-4-trifluoromethyl (2H)-pyrimidinyl)-4-fluorobenzony)t-il. lH -NMR (Do-pyso, 400MH2): 1.28 (s, 3H) , 1.33 (s, 3H), 3.42 (s, 3H), 3.75-3.80 (m, IH), 4.02-4.10 (m% IH), 4.25-4. 43 (ms3H), 6.61CB, IH), 7.90 ((1% IH) , 8.07 (as IH); Similarly, 2-chloro-5-(3,6- Dihi)”0-2,6-thioxo-3-methyl-4-trifluoromethyl-1(2 H)-pyrimidibenzoic acid Starting from benzoic acid, via its acid chloride, 1-cy Using cloprobyl ethanol, 1-cycloprobylethyl 2-chloro-5- (:3.(5-dihydro-2,6-thioxo-3-methyl-4-trifluoromethane) Chill-1(2H)-pyrimidinyl-benzoate. Melting point 118-119 ℃.

Similarly, 2-chloro-5-(3+6-sihydro-2,6-thioxo-3-methane) Tyl-4-pentafluoroethyl-1(2H)l'lJmidinimiso-4-fluoro Starting from lobenzoic acid, via its acid chloride, and tetrahydrofuran-6 -ol, 3-tetrahydrofuryl 2-chloro-5-(3,6-shihyu Draw 2,6-cyoxy-3-methyl-4-pentafluoroethyl-1 (2H) -BilJmisonil)-4-FluoOheyfx)　WII　. lH-NM R(Do-DMSo.

400 MHz): 2. Do-2,09 (rn, IH), 2.2 0-2.32 (ms IH), 3.43 (s% 3H), 3.74- 3.92 (to, 4a), 5.48-5.56 (mslB), 6.50 (ssla), 7-89 (aslH), 8.08 (+1.IH); Similarly, 2-chloro-5-(3,6-sihydro-3,4-dimethyl-2,6 Starting from -dioxo-1(2H)-bilimisonyl]-4-fluorobenzoic acid, By using the following hydroxy compounds, 4-fluorobenzoate, respectively get the same amount.

Using 7-methylcyclopropane, cycloprokylmethyl 2-chloro -5-C3+6-jihi)”.

-3,4-dimethyl-2,6-dioxo1(2)-birimisonyl]-4-ph Obtain fluorobenzoate.

"H-NMR (CDCJ 3.400 MI (Z): 0.31-0-38 (m%2H), 0.57-0.64 (m, 2H), 1.18-1.27 (m, IH), 2.32 (s, 3H), 3.45 (s, 3a), 4.11- 4.15 (m, 2H), 5.74 (s, IH), 7.35 (d, IH), 7.89 (d, IH); Mass spectrum (m/e): M”366 (13); Using 3-hydroxytetrahydrofuran, 3-tetrahydrofuryl 2-k Rollo-5-(3,6-1') obtained. Melting point 149-151°C0 Using 1-cyclopropylethanol, 1-cyclopropylethyl 2-chloro Lo=5-(3,6-sihydro6,4-dimethyl-2,6-dioxo 1(2H )-Birimisonyl]-4-fluorobenzony). IH-NMR (D, -DM80.400 MHz):0.33-0.43 (:n, 2H ), 0.47-0.58 (m, 2H), 1.07-1.17 (mouth, lH) %1.37 (aS3H), 2.33 (s53H), 3.35 (8, 3H), 4.49-4.57 (m, IH), 5.81 (s, IH), 7.8 2 (a % II (), 7.91 (d % IH); Mass spectrum # ( m/e): chloro-5-(3,6-sihydro-3,4-dimethyl-2,6 -Dioxo 1(2)1)-pyrimidinyl]-4-fluorobenzoate with oil and get it. IH-NMR (Da-DMSo, 400 MIHz): 1- 58-1.97 (m% 8H), 2-33 (8% 3H), 3-35 (a , sH), 5.31-5-36 (msIHL5.80 (s, 1H), 7.8 1 (a, IH), 7.91 (alH); Mass spectrum/' (no/e): M”380 (19); Example 2 2-chloro-4-fluoro-5-[2-methoxy-6-oxo-4-trifluoro 3.4 g of lomethyl-1(6H)-pyrimidinyltobenzoic acid was added to dimethylform Reflux temperature in 251 nt of benzene and 5.4 mt of thionyl chloride with 2 drops of amide. Heat for 6 hours. The reaction mixture was then evaporated to dryness and dioxane 20IIIt dissolve in This solution mainly consists of the above acid chloride of benzoic acid and a solvent, and This was combined with 1.0 g of 6-thiethanol and 1.6 g of pyridine in 20 mz of dioxane. Add to the solution of g.

The reaction mixture was then stirred at room temperature for 3.5 hours and treated with 400 mL of water each time. Extract twice with 01d ethyl acetate. The combined organic phases were diluted with 200 g of 1N hydrochloric acid each time. and once with 200 ml of saturated sodium chloride solution, rinse with anhydrous sulfuric acid mug. Dry over nesium and evaporate. The residue was dissolved in diethyl ether/n-hexane ( Purification by chromatography on silica sol using 1:2). this method , chetan-6-yl 2-chloro-4-fluoro-5-[2-methoxy-6 -oxo-4-trifluoromethyl-1(<5I()-1?rimidinyl]-ben The zoate is obtained as a free oil.

'H-NMR (CDCJ3.400 MHz): 3-37-3.44 ( m %2H), 3.57-3.66 (m, 2H), 4.03 (s , 3H), 5.85 (quintQt, IH), 6.63 (s%) IH), 7.42 (a% IH), 7.88 (a, IH).

In a similar manner, 2-chloro-4-fluoro-5-[2-methoxy-6-oxo- Starting from 4-trifluoromethyl-1(6H)pyrimidinyltwobenzoic acid, Via its acid chloride, by reaction with tetrahydrofuran-3-ol, 3 -tetrahydrofuryl 2-chloro-4-fluoro-5-[2-methoxy-6-o 4-trifluoromethyl-1(6I()-pyrimidinyl-to-benzoate get. IH-NMR (r), -DMSo, 400MHz): 2. 02-2-10 (m% IH), 2-20-2-30 (m, IH), 3- 75-3-92 (m-, 4H), 3-96 (s, 3H), 5.48- 5.55 (m, IH), 6.86 (El, IH), 7.95 (a, 1:E(), 8.25 (a, IH), mass spectrum (m/e) :M”436(2).

2-Chloro-4-fluoro-5-(3,6-hydro-2,6-dihydro)-6- Methyl-4-trifluoromethyl-1(2H)-pyrimidinyltobenzoic acid oro Add 3.0 g of potassium Yasutsuko acid and 0.61 nt of shrimp chlorohydrin to dimethyl fluoride. Heat in Lumamide 25 at 70°C for 3 hours. After that, the reaction solution was added to 500 d of water. and adjust to -10 to 11 with a small amount of saturated potassium carbonate solution. Add this to acetic acid. Extract twice at 300 ml. The organic phase was washed twice with 200 ml of water and washed with anhydrous sulfuric acid. Dry over magnesium and concentrate. The residue was purified using ethyl acetate/n-hexane. Purify by chromatography on silica gel. 2,3-epoxypro Biru 2-chloro-5-(3,6-sihydro-2,6-cyoxy-3-methyl- 4-Trifluoromethyl-1(2H)-gyrimisonyl]-4-fluorobenzoe obtained as a pale yellow oil. lH-NMR (D6-DMSo, 400M H2): 2.73 (m, IH)% 2.85 (m% IH), 3 ．． 32 (m s IH), 3.42 (s, 3H), 4.10 (m , IH), 4.69 (m, IH), 6.62 Ca.

IH), 7.92 (a, IH), 8.11 (a% IH) 1, quality Quantity spectrum (m/e): M''422 (16).

Example 4 Earj'rovir 2-chloro-4-fluoro-5-[6,6-sihydro2. 6. -dioxo-4-methyl-1(2H)-pyrimidinyl]-benzoate 14 5.0 g of anhydrous micronized potassium carbonate and 59.0 g of dimethylformamide 1.03g of chlorodiamide was added to the suspension in 11g over 6 hours at 80°C with stirring. Introduce fluoromethane. After cooling, the solid components were separated by suction filtration and 100I+It Rinse with dimethylformamide. The filtrate was highly concentrated under reduced pressure at 55°C. The residue is poured into 21 g of water and the aqueous mixture is adjusted to -3 with concentrated hydrochloric acid.

The mixture was extracted with 1.5 parts of ethyl acetate, the organic phase was washed twice with 11 parts of water each time, Dry over anhydrous sulfuric acid and evaporate to dryness under reduced pressure. Dissolves resinous residue on a 7 Ricadel column using ethyl acetate/n-hexane (1:1) as a release agent. Purify by chromatography. The product was added to 1 sooy of hot n-hexane. The dissolved solution is treated with charcoal powder, filtered and concentrated to 700 ml at high temperature. After that Inoculate the mixture and cool to 5°C while stirring. The crystals formed are filtered off with suction. this Wash with n-hexane and dry. Isopropyl 2-chloro-5-(3-di Fluoromethyl-3,6-cyhydro-2,6-cyoxy-4-methyl-1 (2H )-pyrimidinyl-4-fluorobenzoate, melting point 90-93°C.

Examples 5-8 The corresponding uracil derivatives of formula ■ were combined to form compounds of formula I listed in Table 1 below. For this purpose, alkylation with chlorodifluoromethane is carried out analogously to the procedure described in Example 4.

Example 9 Acetone 201117! 2-chloro-5-[3-difluoromethyl-3,6- Shihydro 2,6-Sio-4-Methyl-1(2H)-pyrimidinyl-4- 2.00 g fluorobenzoic acid, 1.63 g methyl iodide, and sodium carbonate 0.61 f! Heat to boiling point for 4 hours. Then add 1.63g of methyl iodide to Add 1.63.9 to the page 2 hours later. The reaction mixture was heated at reflux temperature for an additional 16 Heat for an hour. After cooling, insoluble components are filtered off with suction, rinsed with acetone, and the filtrate is depressurized. Evaporate to dryness under water. The residue was dissolved in 100 y of ethyl acetate and the solution was heated for 100 r each time. Wash twice with ILt water. Dry the organic phase over anhydrous sodium chloride and evaporate to dryness. Ru. The resinous residue was purified with diethyl ether/n-hexane (1:2) as eluent. Purify by chromatography on a 7 Ricadel column using . the product Recrystallize from diethyl ether/n-hexane. Methyl 2-chloro-5-[ 3-difluoromethyl-3,6-sihydro-2,6-thioxo-4-methyl-1 (2H)l'rimimisol]-4-fluorobenzoate, melting point 121-123° Get C.

Examples 10-19 To prepare the compounds of formula I listed in Table 2 below, a 2-cube procedure similar to that described in Example 9 was carried out. Rolo-5-[3-difluoromethyl-3,6-dihydro-2,6-dioxo4 -Methyl-1(2,I()-pyrimidinyl-4-fluorobenzoic acid) Become a stealth.

Example 20 2-chloro-5-[3-difluoromethyl-3,6-sihydro-2,6-thioxy C-4-methyl-1(2H)-pyrimidinyl-4-fluorobenzoic acid 2.00 A suspension of g and 2.05 # of thionyl chloride in 25 bottles of benzene was refluxed for 20 hours. Heat at temperature. The clear solution is evaporated to dryness at 50° C. under reduced pressure. Methyl chloride residue Dissolve in 20 grams of alcohol, then add 5 grams of propargyl alcohol and 5 grams of propargyl alcohol. Stir with J Gin 0.55 # at room temperature for 3.5 hours. Evaporate the reaction mixture under reduced pressure After drying, the residue was dissolved in 100 g of ethyl acetate, and the solution was diluted with 1 Q [1 mJ of water each time]. Extract 3 times. The organic phase is anhydrous? Dry over sodium chloride and evaporate to dryness. tree The fatty residue was eluted using diethyl ether/n-hexane (1:1). Purify by chromatography on a Clicadell column. propargyl 2- Chloro-5-[31'fluoromethyl-3,6-sihydro-2,6-thioxo 4-Methyl-1(2H)-pyrimidinyl-4-fluorobenzoate is obtained.

IH-NMR (CD (J, 4 [10MHz) near, 94 ppm Cd, IH), 7.71 ppm (t, IH), 7.39 ppm m (a% IH), 5.83 ppm (s, IH), 4.91 ppm (as 2H), 2.52 ppm (t% IH), 2.50 ppm (ms 3H).

Examples 21-25 To prepare the compounds of formula (1) listed in Table 3 below, 2- Chloro-5-[3-difluoromethyl-3,6-sihydro-2,6-thioxo 4-Methyl-1(2H)-pyrimidinyl-4-fluoroprozoic acid is suitably esterified. Tell.

HF2 2.9 g of a 55-60% suspension of sodium hydride in mineral oil was dissolved in dimethylformamide. 301! Add to Lt and 21Lt of toluene, and add to 8 to 0 while stirring the mixture. Cool to °C. 3-amino-4,4,4- in dimethylformamide Z, Qml A solution of 12 g of ethyl trifluorocarboxylate is added. After the addition is complete, pour the mixture into Stir at 5°C for 1 hour. The mixture is then cooled to an internal temperature of -65°C and 7 clopentyl 2-chloro-4-fluoro-5-ink in 33 mj toluene A solution of 10 g of anatobenzoate is fed. The reaction mixture was heated at -65°C for an additional 2. Stir for 5 hours. Then, cyclopentanol was added to this, and the reaction mixture was Warm to room temperature. This was made acidic with glacial acetic acid 1 (1+A) and added to 5Q[]mA of water. The resulting aqueous solution is extracted twice with 250 mt of ethyl acetate each time. Combine the organic phases; Wash once with 200 l of water and 200 l of saturated sodium chloride solution in each case. Clean, dry over anhydrous magnesium sulfate and evaporate under reduced pressure.

The residue was purified using silica sol using ethyl acetate/n-hexane (1:3) as eluent. Purify by chromatography on a column. In this method, cyclopentyl 2 -chloro-5-(3,6-sihydro-2,6-thioxo-4-trifluoromethyl Lu-1(2H)-pyrimidi=k]-4-fluorobenzoate was obtained as a colorless oil. Ru. IH-NMR (CD Cj 3.400 MHz): 1.50-2. 05 (m-, 8H), 5.34-5.48 (m 11H), 6.23 (s, IH), 7.36 (a, IH), 7.85 (a, IH) ; Mass spectrum (m/8): M''420 (1).

Example 27 Cyclopentyl 2-chloro-5-(3,6-cyhydro-2,6-thioxo-4 -trifluoromethyl-1(2H)-bilJmisonyl)-4-fluorobenzoni -) 4.5g, potassium bicarbonate 2.11! and diethyl sulfate 1.5d Heat at reflux temperature for 4 hours in a tube 50+nj. Afterwards, the solvent is distilled off and the residue is diluted. Ethyl ether 150m! , and 150 mt of water. 15 more water phase Extracted with 0 ml of diethyl ether and diluted the combined organic phases with 150 ml of water each time. Wash twice, dry over anhydrous magnesium sulfate, and concentrate. This residue is used as an eluent. Chromatography on a silica gel column using ethyl acetate/n-hexane - Purify it. In this method, cyclopentyl 2-chloro-5-(3-ethyl -3,6-cyhydro-2,6-cyoxy-4-trifluoromethyl-1 (2I ()-pyrimidinyl)-4-fluorobenzoate is obtained as a colorless oil. IH -NMR (CD (u3.400MH2): 1.36 (t, 3H), 1.5 6-2.04 (m, 8H), 4.02 (+1% 2H), 5.3 6-5.45 (m.

1) (), 6.35 (s, IH), 7.3<S (a, IH) , 7.82 (ton 1H); Mass spectrum # (m / e): M" 44 8 (1). Also, cyclopentyl 2-chloro-5-(2-ethquin-6-o xo-4-trifluoromethyl-1(6H)-gyrimisonyl]-4-fluorobe C., melting point 90 DEG-91 DEG C., is also obtained.

Example 28 Isopropyl 2-chloro-5-[3-difluoromethyl] in 60 mt of methylene chloride -3,6-cyhydro-4-methyl-2,6-dioxo-1(2H)-pyrimidine A solution of 18.0 g of Nyl)-4-fluorobenzoate was added to 10011 Lt of concentrated sulfuric acid. Stir vigorously for 5 minutes, then place on ice. The crystals formed are separated by suction filtration, Wash twice with 50 ml of water each time and dissolve in 300 ml of methanol. Mother liquor 1 time each time Extracted twice with 00d methylene chloride, washed the organic phase with water until neutral, and extracted with methanol. Combine with the solution. The solution is dried over anhydrous sodium sulfate and evaporated to dryness.

The crystalline residue was stirred with 100 g of ethyl acetate at 70°C, cooled to room temperature, and allowed to crystallize. The crystals are filtered off with suction and washed with diethyl ether. 2-chloro-5-(3-diflu Olomethyl-6,6-sihydro-4-methyl-2,6-dioxo 1(2H)- Pyrimidinyl-4-fluorobenzoic acid, molten A247-248°C, is obtained.

■ Preparation of benzoic acid ■ and its enol ether - Example 29 Isozorovir in methylene chloride 2Qmt 2-chloro-4-fluoro-5-[2- Methoxy-6-oxo-4-trifluoromethyl-1(6)ri-birimisonyl] - Benzoe) 5F solution was stirred and cooled at 20-25°C while concentrated sulfuric acid 251 Process with nt. The reaction mixture was stirred for an additional 20 minutes at room temperature and poured onto 100 g of ice. ingredient.

The organic phase was separated, the aqueous phase was extracted twice with 15 ml of ethyl acetate each time, and the combined organic Wash the phase with water until neutral.

The solution is then dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure. resinous residue The distillate is crystallized from diethyl ether/n-hexane. 2-chloro-4-fur Oro-5-[2-methoxy-6-oxy-4-trifluoromethyl-1 (6H) -pyrimidinyltwobenzoic acid, melting point 205-210°C.

Similarly, Isoflovir 2-/Clo4-Fluoro-5-[2-Metho-16-Oxo Using 4-pentafluoroethyl-1(6H)-pyrimidinyl-benzoate By doing so, 2-chloro-4-fluoro-5-[2-methoxy-6-oxo -4-Pentafluoroethyl-1(6H)-flimisonyl]-benzoic acid, melting point 1 Obtain 97-199°C.

Isopropyl 2-chloro-4-fluoro-5-[5-fluoro-2-methoxychloride -6-oxo-4-trifluoromethyl-1(6H)-pyrimidinyl-benzo By using ate, 2-chloro-4-fluoro-5-[5-fluoro -2-Methoxy-6-oxo-4-triple-omethyl-1 (6I()-girimi) sonyl]-benzoic acid, melting point 199-201°C.

Isopropyl 2-chloro-4-fluoro-5-[6,6-sihydro2,6- Thioxo-3-methyl-4-trifluoromethyl-1(2H)-ni'limisonil ]-benzoate, 2-chloro-5-(3,6-cyhydro -2,6-di,oxo-3-methyl-4-trifluoromethyl-1(2H)-pi Rimidinyl-4-fluorobenzoate, melting point 239242°C is obtained.

Isopropyl 2-chloro-5-(3,6-sihydro-2,6-thioxo-6- Methyl-4-trifluoromethyl-1(2H)-pyrimidinyl-benzoate 2-chloro-5-(3,(S-dihydro-2,6-thio) Xo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl diamine Obtain fragrant acid, melting point 265-236°C.

Inflovir 2-chloro-5-(3,6-sihydro-2,6-thioxo-6- Methyl-4-pentafluoroethyl-1(2H)-flJmijimiso)-4-flu By using orobenzoate, 2-chloro-5-[3,6-cyhydro -2,6-thioxo-5-methyl-4-pentafluoroethyl-1(2I()- f limisonyl]-4-fluorobenzoic acid, melting point 229-231°C.

Improgyl 2-chloro-5-(3,6-sihydro-6,4-dimethyl-2, Using 6-dioxo 1(2H)-pyrimidinyl-4-fluorobenzoate By using, 2-chloro-5-[3,6-dihydro-6,4-dimethyl- 2,6-Dioxo 1(2I()-pyrimidinyl-4-fluorobenzoic acid, fused Obtain a point of 236-269°C.

Isopropyl 2-chloro-5-(2-methoxy-6-oxo-4-trifluoro By using lomethyl-1(6H)-pyrimidinyl-benzoate, 2-chloro-5-[methoxy-6-oxo-4-trifluoromethyl-1 (6H )-pyrimidinyltwobenzoic acid, melting point 265-268°C.

■Production example 30 of 6-itcyanatobenzoic acid ester of formula 0■ Clopentyl 2-chloro-4-fluoro-5 required as starting material for Example 26 -Ink Anatobenzoate is made by the following process.

2-chloro-4-fluoro-5-2)” benzoic acid 100 g, thionyl chloride 50 A mixture of 100% of alcohol and benzene was added with 0.51% of dimethylformamide. Heat at reflux temperature for 4 hours. After that, the solvent was distilled off, and the crude 2-chloro-4-fluor Oro-5-nitrobenzoyl chloride is obtained as a residue.

This 2-/chlor 4-fluoro-5-nitrobenzoyl chloride was added to 400 pieces of cod. Dissolved in oxane, the solution was 7 clopentanol 36 rIL in 300 g dioxane. t and 42 g of pyridine dropwise with stirring at room temperature. After addition, The mixture was stirred for a further 4 hours at room temperature, added to 300 g of ice and 300 g of 2N hydrochloric acid, Extract twice with 3001d of ethyl acetate each time.

The combined organic phases were saturated once again with 30011 Lt of 2N hydrochloric acid and 15 Qm/each time. ) Extract 6 times with IJum solution, dry over anhydrous magnesium sulfate, and concentrate. . After recrystallization from diisozolobyl ether/n-hexane, cyclopentyl 2 -chloro-4-fluoro-5-nitropenzoate, melting point 44-45°C is obtained.

While stirring in ethanol 190117% water 5Qm/and 32% hydrochloric acid 5- Add 71g of iron powder and heat the whole to 75°C (internal temperature). Add ethyl alcohol to this mixture. Cuclopentyl 2-chloro-4-fluoro-5-nitrobenzo in Nord 50d ) Add a warm solution of 10 Cl dropwise. The reaction mixture was heated to 70-75°G (internal temperature) Stir for another 2 hours, cool, and after cooling, filter on Celite with suction, and filter on a suction filter. Rinse the residue with 5QQd of water followed by 200g of ethyl acetate. This filtrate is saturated Bring to a value of 8 with potassium carbonate solution and filter off the brown precipitate formed on Celite. filtrate was extracted twice with 40 Qd each time of ethyl acetate and the combined organic phases were extracted with 200 Qd each time. +7! Wash twice with saturated sodium chloride solution and dry over anhydrous magnesium sulfate. and concentrate. The residue was then eluted with ethyl acetate/n-hexane (1:4 ) was purified by chromatography on a silica sol column using Crystallize from lobil ether/n-hexane. In this method, cyclopentyl 5 -Amino-2-chloro-4-fluorobenzoate, melting point 61-62°C obtained .

Ethyl acetate 1001n! Medium cyclopentyl 5-amino-2-chloro-4-fur Orobenzoate 19J? A solution of diphosdane 9-7 in ethyl acetate dQmt Add to the solution heated to 0°G (internal temperature) with stirring. Then the reaction mixture Heat at reflux temperature for 2 hours. The solvent was then distilled off and the residue was placed under extremely reduced pressure. distilled in a tube. In this way, the required stock as starting material for Example 26 was obtained. Lopentyl 2-chloro-4-fluoro-5-incyanatobenzoate, boiling point 4 160°C, 10.06w, and approximately Hg.

■, Formulation example Example 31 The emulsifiable concentrate contains the following ingredients; Compound (active substance) according to the present invention 50F/1N-methylpyrrolidone (co-solvent ) 200 g/J nonylphenol (10) ethoxylate) 50&/l (non- ionic emulsifier) Calcium dodecylbenzenesulfonate 2511/11 (anionic emulsifier) Mixture of alkylbenzenes (solvent) in an amount of 1000 m/m active substance and milk Dissolve the oxidizing agent in the co-solvent with stirring and bring the solution to 16 with the solvent.

The resulting emulsifiable concentrate can be emulsified with water, thus achieving the desired concentration. A ready-to-use spray liquid is obtained.

Example 32 Compound (active substance) according to the invention by mixing the following ingredients together to make a 25% spray solution: 25g water silicic acid, (carrier material, grinding agent) 5-259 sodium lauryl nitrate (Wetting agent) 1g sodium lignosulfonate (dispersing agent) 29 kaolin (carrier material) 67-47, F then mix using a Pinzisc mill or equivalent grinding device. Pulverize the mixture.

The resulting spray powder was stirred in water to pass as a ready-to-use spray liquid. A fine suspension is obtained.

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Claims (24)

[Claims] 1. General formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [During the ceremony, R1 is hydrogen, C1-4 alkyl, C3 or 4 alkenyl, C3 or 4 alkyl quinyl, or C1-4 haloalkyl, R2 is a group: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ or when R1 means haloalkyl, hydrogen, C1- 8 alkyl, C2-8 alkenyl, C2-8 alkynyl or C2-8 alkoxy Also means sialkyl, R3 means halogen or cyano, R4 means hydrogen or halogen, R5 means hydrogen, fluorine or C1-4 alkyl, R6 is C1-4 alkyl or C1-4 haloalkyl, The symbols R7 each independently mean hydrogen or C1-3 alkyl, and n means 0, 1 or 2; Q is a saturated 3-membered or 7-membered carbocyclic or atocyclic residue (which may optionally contain one or more C may be substituted with 1 to 4 alkyl groups), but in this case, a heterocyclic residue has one or two heteroatoms selected from oxygen and sulfur and optionally may have a keto functional group within the ring, or Q means a phenyl group, and this phenyl group optionally contains halogen, C1- 4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 alkylti Even if it is mono-substituted or polysubstituted by o, nitro and/or cyano Often, and can further include fused saturated carbocyclic or heterocyclic 5- to 7-membered rings. - and this heterocycle has one or two oxygen atoms in the ring] as well as compounds of formula I (wherein R1 is different from hydrogen or C1-4 haloalkyl) as well as the corresponding enol ether of the compound of formula I (wherein R1 or R 2 means hydrogen). 2. R1 is hydrogen, C1-4 alkyl, C3 or 4 alkenyl or C3 or 4-alkynyl compounds according to claim 1, and their enoyl ether and salt. 3. R1 means C1-4 haloalkyl, R2 is hydrogen, C1-8 alkyl, C 2-8 alkenyl, C2-8 alkynyl, C2-8 alkoxyalkyl or - (CR7R7) means n-Q, where Q is a saturated 3- to 7-membered carbocyclic or heterocyclic residue and this group is optionally one or more C1-4 alkyl groups. Optionally substituted, the heterocyclic residue has a ring selected from oxygen or sulfur. or Q means a phenyl group, and The phenyl group of the lever is halogen, C1-4 alkyl, C1-4 haloalkyl, C1 ~4 alkoxy, C1-4 alkylthio, nitro and/or cyano The compound according to claim 1, which may be mono- or polysubstituted by combination. compounds and salts of these compounds. 4. 3. A compound according to claim 2, wherein R1 means methyl. 5. 4. A compound according to claim 3, wherein R1 means difluoromethyl. 6. Claim 1, wherein R3 means chlorine or bromine and R4 means fluorine. The compound according to any one of Items 1 to 5. 7. Claim 1, in which R3 means chlorine or bromine and R4 means hydrogen The compound according to any one of Item 6 above. 8. Claims 1 to 7, wherein R5 means hydrogen, fluorine or methyl The compound according to any one of . 9. Any of claims 1 to 8, wherein R6 means C1-4 alkyl The compound according to item 1. 10. R2 is a group -(CR7R7)n-Q (wherein each R7 means hydrogen and n is 0 or 1) according to any one of claims 1 to 9. Compounds described in. 11. cyclohebutyl 2-chloro-5-[3,6-dihydro-2,6-dioxo -3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-ph luolobenzoate, 3-tetrahydrofuryl 2-chloro-5-[3,6-dihydro-2,6-diox -3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4- fluorobenzoate, 1,3-dioxan-5-yl 2-chloro-5-[3,6-dihydro-2,6- dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl] -4-fluorobenzoate, cyclopropylmethyl 2-chloro-5-[3,6-dihydro-2,6-dio group -3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-ph luolobenzoate, Tetrahydrofurfuryl 2-chloro-5-[3,6-dihydro-2,6-diox -3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4- fluorobenzoate, 1,3-dioxolan-4-ylmethyl 2-chloro-5-[3,6-dihydro- 2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimi [dinyl]-4-fluorobenzoate, benzyl 2-chloro-5-[3,6-di Hydro-2,6-dioquine-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidinyl]-4-fluorobenzoate, 4,4-dimethyl-2-oxo-tetrahydrofuran-3-yl 2-chloro-5 -[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethi Ru-1(2H)-pyrimidinyl]-4-fluorobenzoate, Cyclobentyl 2-chloro-5-[3,6-dihydro-2,6-dioxo-3- Methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-fluoro benzoate, 1-Cyclopropylethyl 2-chloro-5-[3,6-dihydro-2,6-dio xo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4 - fluorobenzoate, and Cyclohexyl 2-chloro-5-[3,6-dihydro-2,6-dioquine-3- Methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-fluoro benzoate The compound according to claim 2, selected from: 12. Isopropyl 2-chloro-5-[3-difluoromethyl-3,6-dihyde rho-4-methyl-2,6-dioxo-1(2H)-pyrimidinyl]-4-fluoro lobenzoate, 2-chloro-5-[3-difluoromethyl-3,6-dihydro-4-methyl-2 , 6-dioxo-1(2H)-pyrimidinyl]-4-fluorobenzoic acid, isop Lopyl 5-[4-ethyl-3-difluoromethyl-3,6-dihydro-2,6- Dioxo-1(2H)-pyrimidinyl]-2-chloro-4-fluorobenzoate to, Isopropyl 5-[4-ethyl-3-difluoromethyl-3,6-dihydro-2 ,6-dioxo-1(2H)-pyrimidinyl]-2-promo-4-fluoroben zoate, Inpropyl 2-promo-5-[3-difluoromethyl-3,6-dihydro-4 -Methyl-2,6-dioquine-1(2H)-pyrimidinyl]-4-fluoroben zoate, 2-provinyl 2-chloro-5-[3-difluoromethyl-3,6-dihydro- 4-Methyl-2,6-dioxo-1(2H)-pyrimidyl]-4-fluorobe Inzoate, Kayobi Methyl 2-chloro-5-[3-difluoromethyl-3,6-dihydro-4-methy -2,6-dioxo-1(2H)-pyrimidinyl]-4-fluorobenzoe to The compound according to claim 3, selected from: 13. Cyclopropylmethyl 2-chloro-5-[3,6-dihydro-3,4-di Methyl-2,6-dioquine-1(2H)-pyrimidinyl]-4-fluorobenzo Eight, 1-Cyclopropylethyl 2-chloro-5-[3,6-dihydro-3,4-dimethyl Chil-2,6-dioxo-1(2H)-pyrimidinyl]-4-fluorobenzoe tort, cyclobentyl 2-chloro-5-[3,6-dihydro-3,4-dimethyl-2, 6-dioxo-1(2H)-pyrimidyl]-4-fluorobenzoate, lohexyl 2-chloro-5-[3,6-dihydro-3,4-dimethyl-2,6- Dioquin-1(2H)-pyrimidinyl]-4-fluorobenzoate, cyclohe Butyl 2-chloro-5-[3,6-dihydro-3,4-dimethyl-2,6-dio xo-1(2H)-pyrimidinyl]-4-fluorobenzoate, 3-tetrahydryl Drofuryl 2-chloro-5-[3,6-dihydro-3,4-dimethyl-2,6- dioxo-1(2H)-pyrimidinyl]-4-fluorobenzoate, 1,3-dioxan-5-yl 2-chloro-5-[3,6-dihydro-3,4- Dimethyl-2,6-dioquine-1(2H)-pyrimidinyl]-4-fluoroben zoate, (1,3-dioxolan-4-yl)methyl 2-chloro-5-[3,6-dihydro rho-3,4-dimethyl-2,6-dioquine-1(2H)-pyrimidinyl]-4- fluorobenzoate, Benzyl 2-chloro-5-[3,6-dihydro-3,4-dimethyl-2,6-di Oxo-1(2H)-pyrimidinyl]-4-fluorobenzoate, and tet Lahydrofurfuryl 2-chloro-5-[3,6-dihydro-3,4-dimethyl- 2,6-dioxo-1(2H)-pyrimidinyl]-4-fluorobenzoate A compound according to claim 1, selected from: 14. General formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1' is C1-4 alkyl, C3 or 4 alkenyl, or C3 or 4 alkyl means quinyl; R3 means halogen or cyano, R4 means hydrogen or halogen, R5 means hydrogen, fluorine or C1-4 alkyl, R6 is C1-4 alkyl or C1-4 haloalkyl) and its salts. 15. General formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [During the ceremony, R1 is hydrogen, C1-4 alkyl, C3 or 4 alkenyl, C3 or 4 alkyl Nyl, or C1-4 haloalkyl, R2 is a group: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ or when R1 means haloalkyl, hydrogen, C1- 8 alkyl, C2-8 alkenyl, C2-8 alkynyl or C2-8 alkoxy Also means sialkyl, R3 means halogen or cyano, R4 means hydrogen or halogen, R5 means hydrogen, fluorine or C1-4 alkyl, R6 is C1-4 alkyl or C1-4 haloalkyl, The symbols R7 each independently mean hydrogen or C1-3 alkyl, and n means 0, 1 or 2; Q is a saturated 3- to 7-membered negative carbocyclic or heterocyclic residue (which optionally contains one or more C may be substituted with 1 to 4 alkyl groups), but in this case, a heterocyclic residue has one or two heteroatoms selected from oxygen and sulfur, and in some cases may have a keto functional group within the ring, or Q means a phenyl group, and this phenyl group is optionally halogen, C1- 4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 alkylthi monosubstituted or polysubstituted with nitro, nitro, and/or cyano. Often, and may further include fused saturated carbocyclic or heterocyclic 5- to 7-membered rings. and this heterocycle has one or two oxygen atoms in the ring. at least one compound containing Such compounds I (wherein R1 is different from hydrogen or C1-4 haloalkyl) or of such compounds I in which R1 or R2 is hydrogen. A weed control composition containing an effective amount of salt as well as a formulation aid. 16. The following group of compounds, cyclohebutyl 2-chloro-5-[3,6-dihydro-2,6-dioxo-3- Methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-fluoro benzoate, 3-tetrahydrofuryl 2-chloro-5-[3,6-dihydro-2,6-diox -3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4- fluorobenzoate, 1,3-dioxan-4-yl 2-chloro-5-[3,6-dihydro-2,6- dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl] -4-fluorobenzoate, cyclopropylmethyl 2-chloro-5-[3,6-dihydro-2,6-dioquine -3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-ph luolobenzoate, Tetrahydrofurfuryl 2-chloro-5-[3,6-dihydro-2,6-diox So-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4- fluorobenzoate, 1,3-dioxolan-4-ylmethyl 2-chloro-5-[3,6-dihydro- 2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimi [dinyl]-4-fluorobenzoate, benzyl 2-chloro-5-[3,6-di Hydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidinyl]-4-fluorobenzoate, 4,4-dimethyl-2-oxo-tetrahydrofuran-3-yl 2-chloro-5 -[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethi Ru-1(2H)-pyrimidinyl]-4-fluorobenzoate, Cyclobentyl 2-chloro-5-[3,6-dihydro-2,6-dioxo-3- Methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-fluoro benzoate, 1-Cyclopropylethyl 2-chloro-5-[3,6-dihydro-2,6-dio xo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4 - fluorobenzoate, and Cyclohexyl 2-chloro-5-[3,6-dihydro-2,6-dioquine-3- Methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-fluoro benzoate Claims containing an effective amount of at least one compound selected from: The weed control composition according to item 15. 17. The following group of compounds, Isopropyl 2-chloro-5-[3-difluoromethyl-3,6-dihydro-4 -Methyl-2,6-dioxo-1(2H)-pyrimidinyl]-4-fluoroben zoate, 2-chloro-5-[3-difluoromethyl-3,6-dihydro-4-methyl-2 , 6-dioquine-1(2H)-pyrimidinyl]-4-fluorobenzoic acid, isop Lopyl 5-[4-ethyl-3-difluoromethyl-3,6-dihydro-2,6- Dioxo-1(2H)-pyrimidinyl]-2-chloro-4-fluorobesozoe to, Isopropyl 5-[4-ethyl-3-difluoromethyl-3,6-dihydro-2 ,6-dioxo-1(2H)-pyrimidinyl]-2-promo-4-fluoroben zoate, Isopropyl 2-promo-5-[3-difluoromethyl-3,6-dihydro-4 -Methyl-2,6-dioxo-1(2H)-pyrimidinyl]-4-fluoroben zoate, 2-provinyl 2-chloro-5-[3-difluoromethyl-3,6-dihydro- 4-Methyl-2,6-dioxo-1(2H)-pyrimidinyl]-4-fluorobe ndzoate, and Methyl 2-chloro-5-[3-difluoromethyl-3,6-dihydro-4-methy -2,6-dioxo-1(2H)-pyrimidinyl]-4-fluorobenzoate to containing an effective amount of at least one compound selected from: The weed control composition according to claim 15. 18. The following group of compounds, cyclopropylmethyl 2-chloro-5-[3,6-dihydro-3,4-dimethyl -2,6-dioquine-1(2H)-pyrimidinyl]-4-fluorobenzoate , 1-Cyclopropylethyl 2-chloro-5-[3,6-dihydro-3,4-dimethyl Chil-2,6-dioxo-1(2H)-pyrimidinyl]-4-fluorobenzoe tort, cyclobentyl 2-chloro-5-[3,6-dihydro-3,4-dimether-2, 6-dioxo-1(2H)-pyrimidinyl]-4-fluorobenzoate, Rohekyl 2-chloro-5-[3,6-dihydro-3,4-dimethyl-2,6- Dioquin-1(2H)-pyrimidinyl]-4-fluorobenzoate, cyclohe Butyl 2-chloro-5-[3,6-dihydro-3,4-dimethyl-2,6-dio xo-1(2H)-pyrimidinyl]-4-fluorobenzoate, 3-tetrahydryl Drofuryl 2-chloro-5-[3,6-dihydro-3,4-dimethyl-2,6- dioxo-1(2H)-pyrimidinyl]-4-fluorobenzoate, 1,3-dioxan-5-yl 2-chloro-5-[3,6-dihydro-3,4- Dimethyl-2,6-dioxo-1(2H)-pyrimidinyl]-4-fluoroben zoate, (1,3-dioxolan-4-yl)methyl 2-chloro-5-[3,6-dihydro rho-3,4-dimethyl-2,6-dioxo-1(2H)-pyrimidinyl]-4- fluorobenzoate, Benzyl 2-chloro-5-[3,6-dihydro-3,4-dimethyl-2,6-di Oxo-1(2H)-pyrimidinyl]-4-fluorobenzoate, and tet Lahydrofurfuryl 2-chloro-5-[3,6-dihydro-3,4-dimether- 2,6-dioxo-1(2H)-pyrimidinyl]-4-fluorobenzoate containing an effective amount of at least one compound selected from as well as formulation adjuvants; The weed control composition according to claim 15. 19. General formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1' is C1-4 alkyl, C3 or 4 alkenyl or C3 or 4 alkyl means nil; R3 means halogen or cyano, R4 means hydrogen or halogen, R5 means hydrogen, fluorine, or C1-4 alkyl, and R6 means C1-4 alkyl. or C1-4 haloalkyl) an effective amount of at least one compound represented by or a salt thereof, and a formulation aid A weed control composition containing the agent. 20. general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [During the ceremony, R1 is hydrogen, C1-4 alkyl, C3 or 4 alkenyl, C3 or 4 alkyl Nyl, or C1-4 haloalkyl, R2 is a group: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ or when R1 means haloalkyl, hydrogen, C1- 8 alkyl, C2-8 alkenyl, C2-8 alkynyl or C2-8 alkoxy Also means sialkyl, R3 means halogen or cyano, R4 means hydrogen or halogen, R5 means hydrogen, fluorine or C1-4 alkyl, R6 is C1-4 alkyl or C1-4 haloalkyl, The symbols R7 each independently mean hydrogen or C1-3 alkyl, and n means 0, 1 or 2; Q is a saturated 3- to 7-membered carbocyclic or heterocyclic residue (which optionally contains one or more C may be substituted with 1 to 4 alkyl groups]; in this case, a heterocyclic residue has one or two heteroatoms selected from oxygen and sulfur and optionally a ring has a keto functional group in the Q means a phenyl group, and this phenyl group optionally contains halogen, C1-4 Alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 alkylthio , may be mono- or polysubstituted by nitro and/or cyano. and can further include fused saturated carbocyclic or heterocyclic 5- to 7-membered rings. , and this heterocycle has one or two oxygen atoms in the ring] compounds of formula I, where R1 is different from hydrogen or C1_4 haloalkyl ) as well as the corresponding enol ether of the compound of formula I (wherein R1 or R2 is In the method for producing a salt of a compound (meaning hydrogen), (a) Compounds of formula I in which R1 represents hydrogen and, if necessary, gold of these compounds. In order to produce genus salts, the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R3, R4, R5, R6, R7, n and Q have the above meanings, R8 means lower alkyl] is cyclized under basic conditions, and the necessary Accordingly, the acid form ( (b) In formula I, R1 is C1-4 alkyl, C3 or or 4 alkenyl, C3 or 4 alkynyl or C1-4 haloalkyl and when R1 means C1-4 haloalkyl, R2 is a radical different from hydrogen. To produce the compound, the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R2, R3, R4, R5 and R6 have the above meanings, but R1 When preparing compounds of formula I in which represents C1-4 haloalkyl, in formula I' with the proviso that R2 is different from hydrogen), C1-4 Pairs containing alkyl, C3 or 4 alkenyl, or C3 or 4 alkynyl groups alkylated with a corresponding alkylating agent, (c) For producing compounds of formula I in which R1 is not hydrogen and the corresponding enol ethers. In order to understand, there are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R3, R4, R5, and R6 have the above meanings, and R1'' is C1~ 4 alkyl, C3 or 4 alkenyl, C3 or 4 alkynyl or C1~ benzoic acid with the general formula R2OHIV (In the formula, R2 has the above meaning, except that R1 means C1-4 haloalkyl. When preparing compounds of formula I, it is provided that R2 in formula IV is different from hydrogen. esterification with a hydroxy compound having a esterification with reactive derivatives of xyl compounds, (d) In order to produce a compound of formula I in which R1 is different from hydrogen, the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1'', R3, R4, R5 and R6 have the above meanings, and R9 is C 1-6 alkyl, C2-4 alkenyl, C2-4 alkynyl or C2-6 alkyl benzoic acid ester of the formula IV above, xy compound (Reagent IV is alkanol, alkanol or alkynol R8O (having a boiling point higher than H), or (e) Compounds of formula I in which R1 represents C1-4 haloalkyl and R2 represents hydrogen; In order to manufacture, there are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R3, R4, R5 and R6 have the above meanings, and R11''' is C1 〜4haloalkyl, R2' has the meaning of R2, but excludes hydrogen ) is hydrolyzed to give the corresponding benzoic acid, and (f) formula I To prepare the enol ether of the compound, the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R3, R4, R5, R6, R7, n and Q have the above meanings, Ha l means chlorine or bromine) in the presence of an organic base. treatment with lukanol, alkanol or alkynol R1'OH or is a general formula R1'O-M+ VII (wherein R1' has the above meaning and M+ means an equivalent metal ion) with the corresponding alcoholate, alkinolate or alkinolate and as required. If necessary, the thus obtained formula I [wherein R1 or R2 means hydrogen] Converting the compound of (a) into a salt. 21. general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1' is C1-4 alkyl, C3 or 4 alkenyl or C3 or 4 alkyl means nil; R3 means halogen or cyano, R4 means hydrogen or halogen, R5 means hydrogen, fluorine, or C1-4 alkyl, and R6 means C1-4 alkyl. or C1-4 haloalkyl) and salts thereof In law, the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1', R3, R4, R5 and R6 have the above meanings, and R9 is C1 ~6 alkyl, C2_4 alganyl, C2_4 alkynyl or C2_6 alkyl meaning xyalkyl] is subjected to hydrolysis, and if necessary, this compound is subjected to hydrolysis. The above process for converting the compound of formula IIIa thus obtained into a salt. 22. In the claims, R6 means in each case C1-4 alkyl, especially methyl. The method according to item 20 or 21. 23. The location and/or weeds to be protected from weeds are defined from claim 1. The compound according to any one of item 14 or claims 15 to 19 A method for controlling weeds, comprising treating with an effective amount of the composition according to any one of paragraphs. 24. The compound or claim according to any one of claims 1 to 14 For weed control using the composition according to any one of Items 15 to 19 Use of.